Plastic material surface treatment with a polymerizable and/or crosslinkable organic composition having reactive functions

ABSTRACT

The invention concerns a method for treating the surface of a plastic material comprising the following steps: (1) applying on at least one of the surfaces of the plastic material a composition with polymerizable and/or crosslinkable reactive functions comprising: 1 to 99 wt. % of at least a polymerizable and/or at least partially polymerized silicone matrix A, including (co)monomers, (co)oligomers and/or (co)polymers selected among those having oxetane functions (frA); 99 to 1 wt. % of at least a polymerizable and/or at least partially polymerized matrix B, including (co)monomers, (co)oligomers and/or (co)polymers selected among those having epoxy (α 1 ), and/or acrylate (α 2 ) and/or alkenyl-ether (α 3 ) and/or hydroxyl (α 4 ) reactive functions (frB); and efficient amount of at least a cationic or cationic and radical initiator system C; and optionally at least a sensitizer D and at least a pigment E; (2) polymerizing and/or crosslinking the treated surface under an irradiating source and/or under electron beam(s).

The field of the invention is that of the surface treatment of plastics based on silicone compositions which can be crosslinked and/or polymerized under irradiation, in particular under UV irradiation and/or by an electron beam. More specifically, the invention relates to the plastic surface treated for the purpose of forming a silicone coating, such as an ink, a nonstick coating, an adhesive coating or a varnish.

Plastics are increasingly used as packagings, such as containers, in particular cases, bottles and sachets. These plastics can be transparent, translucent, colored or opaque and are generally based on polyethylene, on polypropylene, on polystyrene and/or on polyester.

The development of a surface treatment for coating plastics is complex and requires specific qualities of adhesion, of robustness, of flexibility, of resistance to scratching, of resistance to twisting, of resistance to water and of resistance to stains.

To date, however, technologies, in particular those for thermal drying of systems often based on products carried in solvents, are not suitable for efficiently treating plastic surfaces and for retaining, in particular over time and during the handling thereof, the qualities which are necessary for it.

The present invention proposes to overcome the existing shortcomings in the field of the surface treatment of plastics. One of the essential objectives of the present invention is therefore to provide a novel process for the surface treatment of plastics with a silicone composition which can be crosslinked and/or polymerized by the cationic route or by the cationic and radical route which meets these expectations.

The present invention relates to a novel process for the surface treatment of a plastic for the purpose of forming a coating comprising the following stages:

-   -   (1) application, to at least one of the surfaces of the plastic,         of a composition with reactive functional groups which can be         polymerized and/or crosslinked by the cationic route or by the         cationic and radical route comprising:         -   1 to 99% by weight, and preferably 1 to 60% by weight, of at             least one polymerizable and/or at least partially             polymerized silicone matrix A comprising (co)monomers,             (co)oligomers and/or (co)polymers selected from those having             oxetane reactive functional groups (Arf),         -   99 to 1% by weight, and preferably 99 to 40% by weight, of             at least one polymerizable and/or at least partially             polymerized matrix B comprising (co)monomers, (co)oligomers             and/or (co)polymers selected from those having epoxy (α₁)             and/or acrylate (α₂) and/or alkenyl ether (α₃) and/or             hydroxyl (α₄) reactive functional groups (Brf),         -   an effective amount of at least one cationic or cationic and             radical initiator system C,         -   optionally at least one sensitizer D,         -   and optionally at least one pigment E;     -   (2) and polymerization and/or crosslinking of the treated         surface by its exposure under a source of irradiation and/or         under electron beam(s).

This novel type of treatment confers on plastics, and more particularly polypropylene, appropriate surface qualities as regards adhesion, robustness, flexibility, resistance to scratching, resistance to twisting, resistance to water, resistance to stains, absence of shrinkage in volume and, in particular for transparent coatings obtained, absence of yellowing.

The exposure under a source of irradiation is generally carried out under UV radiation. More particularly, use is made of UV radiation with a wavelength of the order of 200 to 500 nm.

Preferably, the matrix A with oxetane reactive functional groups (Arf) used within the composition according to the process of the invention is based on highly varied (co)monomers, (co)oligomers and/or (co)polymers of silicone nature. In this respect, the (co)monomers, (co)oligomers and/or (co)polymers of at least one of the following polyorganosiloxane species A1) are particularly suitable, which (co)monomers, (co)oligomers and/or (co)polymers are composed of units of formula (II) and are terminated by units of formula (III) or are cyclic and are composed of units of formula (II), which formulae are represented below:

in which:

-   -   the R⁶ and R⁷ symbols, which are alike or different, represent:         -   a linear or branched alkyl radical comprising 1 to 8 carbon             atoms which is optionally substituted by at least one             halogen, preferably fluorine, the alkyl radicals preferably             being methyl, ethyl, propyl, octyl and             3,3,3-trifluoropropyl,         -   a cycloalkyl radical comprising between 5 and 8 cyclic             carbon atoms, which radical is optionally substituted,         -   an aryl radical comprising between 6 and 12 carbon atoms,             which radical can be substituted, preferably phenyl or             dichlorophenyl,         -   an aralkyl radical having an alkyl part comprising between 5             and 14 carbon atoms and an aryl part comprising between 6             and 12 carbon atoms, which part is optionally substituted on             the aryl part by halogens, alkyls and/or alkoxyls comprising             1 to 3 carbon atoms,     -   the Z symbols, which are alike or different, represent:         -   an R⁶ and/or R⁷ group,         -   a hydrogen radical,         -   and/or a crosslinkable oxetane functional group connected to             the silicon of the polyorganosiloxane via a divalent radical             which comprises from 2 to 20 carbon atoms and which can             comprise at least one heteroatom, preferably oxygen, it             being possible for the latter to be bonded directly to the             silicon, forming an ≡Si—OC≡ bond,         -   with at least one of the Z symbols representing a             crosslinkable oxetane functional group.

According to an advantageous alternative form of the invention, the polyorganosiloxanes A1 used comprise from 1 to 10 organofunctional groups per macromolecular chain.

These linear polyorganosiloxanes can be oils with a dynamic viscosity at 25° C. of the order of 10 to 10 000 mPa.s at 25° C., generally of the order of 20 to 5000 mPa.s at 25° C. and more preferably still of 20 to 600 mPa.s at 25° C., or gums exhibiting a molecular mass of the order of 1 000 000.

When the polyorganosiloxanes are cyclic polyorganosiloxanes, the latter are composed of units (II) which can, for example, be of the dialkylsiloxy or alkylarylsiloxy type. These cyclic polyorganosiloxanes exhibit a viscosity of the order of 1 to 5000 mPa.s.

Mention may be made, as examples of an organofunctional radical of the oxetane type connected to the backbone of the polyorganosiloxane A1, of the group of following formula:

The oxetane functional polyorganosiloxanes can be prepared by hydrosilylation of unsaturated oxetanes or condensation of oxetanes including a hydroxyl functional group.

The polyorganosiloxanes A1 corresponding best to the subject matter of the invention are described in the formulae below. X can represent an alkyl, cyclohexyl, trifluoropropyl, perfluoroalkyl, alkoxy or hydroxypropyl group and R can represent a C₁ to C₁₀ alkyl, cyclohexyl, trifluoropropyl or C₁ to C₁₀ perfluoroalkyl radical and (0≦a≦1 000); (1≦b≦1 000);

In addition to species of silicone nature, the matrix A can comprise (co)monomers, (co)oligomers and/or (co)polymers of organic natures, which (co)monomers, (co)oligomers and/or (co)polymers are composed of at least one of the species of following formulae:

-   -   A2) monomers with oxetane and alkoxy functional groups, oxetane         and hydroxyl functional groups, or oxetane and alkoxysilyl         functional groups of formula:     -    in which:         -   R₁ is (i) a hydrogen atom; (ii) a linear or branched alkyl             radical comprising from 1 to 30 carbon atoms; (iii) an aryl             radical comprising from 6 to 30 carbon atoms, which radical             is optionally substituted by at least one fluorine atom, one             carboxyl radical, one hydroxyl radical, one ester radical or             one radical with a ketone functional group; (iv) a             cycloalkyl radical comprising from 5 to 6 carbon atoms,             which radical is optionally substituted by at least one             fluorine atom, one hydroxyl radical, one carboxyl radical,             one ester radical or one radical with a ketone functional             group; (v) an OR′ radical where R′ is a linear or branched             alkyl radical comprising from 1 to 30 carbon atoms; or (vi)             an alkenyl radical comprising from 2 to 12 carbon atoms,         -   R₂ is (i) a hydrogen atom; (ii) an alkenyl radical             comprising from 2 to 12 carbon atoms (for example a vinyl             radical or a propenyl radical); (iii) a linear or branched             alkyl-radical comprising from 1 to 30 carbon atoms, which             radical is optionally substituted, for example by an oxirane             group; (iv) an aryl radical comprising from 6 to 30 carbon             atoms, which radical is optionally substituted, for example             by at least one alkyl radical comprising from 1 to 30 carbon             atoms, one benzyl radical, one CF₃ radical, one halogen             atom, one hydroxyl radical, one carboxyl radical or one             alkoxy radical; (v) a linear or branched alkylated and             silylated or silylated group —(C_(n)H_(2n))—SiR₃R₄R₅, where             n is between 1 and 12 and R₃, R₄ and R₅, which are identical             or different, represent a hydrogen atom, a hydroxyl radical             or an alkoxy radical OR′ where R′ is a linear or branched             alkyl radical comprising from 1 to 30 carbon atoms; (vi) a             linear or branched alkyl radical comprising from 1 to 30             carbon atoms; (vii) an aryl radical comprising from 6 to 30             carbon atoms, which radical is optionally             substituted; (viii) an alkenyl radical comprising from 2 to             12 carbon atoms; (ix) an acrylate radical; (x) a             methacrylate radical (for example —CO—CH═CH₂; or (xi) a             urethane radical —CO—NH—R₁ in which R₁ has the same             definition as that given above,     -   A3) monomers comprising carboxyl and oxetane functional groups         or comprising oxetane and alkoxysilyl functional groups of         formula:     -    in which:         -   R₁ has a definition identical to that given in A2),         -   R₂ has a definition identical to that given in A2);     -   A4) difunctional oxetane monomers of formula:     -    in which:         -   m, which is identical or different, is equal to 0 or 1,         -   R₁ has a definition identical to that given in A2),         -   R₆, a divalent radical, is (i) a linear or branched alkyl             radical comprising from 1 to 30 carbon atoms; (ii) an aryl             radical comprising from 6 to 30 carbon atoms, which radical             is optionally substituted (by at least one alkyl radical             comprising from 1 to 30 carbon atoms; (iii) an aryl radical             comprising from 6 to 30 carbon atoms (for example a benzyl             radical); (iv) a cycloalkyl radical comprising from 5 to 30             carbon atoms (ex.: cyclohexyl); (v) a —CH₂—C₆H₁₀—CH₂—             radical; (vi) a —CH₂—C₆H₄—CH₂— radical; (vii) a CF₃             radical; (viii) a halogen atom; (ix) a hydroxyl radical; (x)             a carboxyl radical; (xi) an alkoxy radical OR′ where R′ has             a definition identical to that given in A2); (xii) a silyl             group ═SiR₃R₄ where n is between 0 and 12 and R₃ and R₄,             which are identical or different, represent a hydrogen atom,             a hydroxyl radical, an alkoxy radical OR′ where R′ has a             definition identical to that given in A2), a linear or             branched alkyl radical comprising from 1 to 30 carbon atoms,             an aryl radical comprising from 6 to 30 carbon atoms which             is optionally substituted, a —C₆H₄—C(CH₃)₂—C₆H₄— radical or             an alkenyl radical comprising from 2 to 12 carbon atoms.

Mention will be made, as examples of species A2, of those of following formulae:

Mention will be made, as examples of species A3, of those of following formulae:

Mention will be made, as species A4, of those of following formulae:

As regards the matrix B, the latter can comprise in particular at least one of the following organic species B1:

-   α_(1.1)) cycloaliphatic epoxides and in particular:     -   epoxides of the 3,4-epoxycyclohexylmethyl         3′,4′-epoxycyclohexanecarboxylate type:     -   or bis(3,4-epoxycyclohexyl) adipate; -   α_(1.2)) noncycloaliphatic epoxides and in particular:     -   epoxides of the type of those resulting from the condensation of         bisphenol A and of epichlorohydrin and of the type:         -   di- and triglycidyl ethers of bisphenol A alkoxylated with             1,6-hexanediol, with glycerol, with neopentyl glycol and             with trimethylolpropane,         -   or diglycidyl ethers of bisphenol A,     -   α-olefin epoxides, novolac epoxides, epoxidized soybean oil,         epoxidized linseed oil and epoxidized polybutadiene, -   α₂) acrylates, and in particular:     -   epoxidized acrylates, preferably the oligomer of bisphenol A         epoxydiacrylate (Ebecryl 600),     -   polyester glycerol acrylates, preferably a mixture of oligomer         of acrylate which is trifunctional obtained from glycerol and         polyester (Ebecryl 810),     -   multifunctional acrylates, preferably pentaerythritol         triacrylate (PETA), trimethylolpropane triacrylate (TMPTA),         1,6-hexanediol diacrylate (HDODA), trimethylolpropane ethoxylate         triacrylate, thiodiethylene glycol diacrylate, tetraethylene         glycol diacrylate (TTEGDA), tripropylene glycol diacrylate         (TRPGDA), triethylene glycol diacrylate (TREGDA),         trimethylpropane trimethacrylate (TMPTMA), dipentaerythritol         pentaacrylate and pentaerythritol ethoxylate tetraacrylate,     -   urethane acrylates,     -   polyether acrylates,     -   polyester acrylates,     -   unsaturated polyesters,     -   acrylic acrylates, -   α₃) linear or cyclic alkenyl ethers and in particular:     -   vinyl ethers, in particular dodecyl vinyl ether (DDVE),         cyclohexyl vinyl ether (CVE), butanediol divinyl ether (BDVE),         butanediol monovinyl ether (HBVE), cyclohexanedimethanol divinyl         ether (CHDVE), cyclohexanedimethanol monovinyl ether (CHMVE),         triethylene glycol divinyl ether (DVE-3) and vinyl ethers of         formula:     -   propenyl ethers,     -   and butenyl ethers; -   α₄) polyols, and preferably the compound of formula:

In addition to the organic species B1, the matrix B can also comprise or be based on monomer(s), (co)oligomer(s) and/or (co)polymer(s) of polyorganosiloxanes nature B2, which monomer(s), (co)oligomer(s) and/or (co)polymer(s) are composed of units of formula (IV) and are terminated by units of formula (V) or are cyclic and are composed of units of formula (IV), which formulae are presented below:

-   -   in which:         -   the R⁶ and R⁷ symbols, which are alike or different, have             definitions identical to those given for A1 on pages 4 to 5,         -   the Z′ symbols, which are alike or different, represent:             -   an R⁶ and/or R⁷ group,             -   a hydrogen radical,             -   and/or a crosslinkable organofunctional group,                 preferably an epoxy functional, dioxolane functional                 and/or alkenyl ether functional group, connected to the                 silicon of the polyorganosiloxane via a divalent radical                 which comprises from 2 to 20 carbon atoms and which can                 comprise at least one heteroatom, preferably oxygen,             -   with at least one of the Z′ symbols representing a                 crosslinkable organic functional group.

According to an advantageous alternative form of the invention, the polyorganosiloxanes B2 used comprise from 1 to 10 organofunctional groups (Brf) per macromolecular chain. For an epoxy functional group, this corresponds to epoxide levels varying from 20 to 2 000 molar meq/100 g of polyorganosiloxane.

The linear polyorganosiloxanes B2 can be oils with a dynamic viscosity at 25° C. of the order of 10 to 10 000 mPa.s at 25° C., generally of the order of 20 to 5 000 mPa.s at 25° C. and more preferably still of 20 to 600 mPa.s at 25° C., or gums exhibiting a molecular mass of the order of 1 000 000.

In the case of cyclic polyorganosiloxanes B2, the latter are composed of units (IV) which can, for example, be of the dialkylsiloxy or alkylarylsiloxy type. These cyclic polyorganosiloxanes exhibit a viscosity of the order of 1 to 5 000 mPa.s.

Mention may be made, as examples of organofunctional groups (Brf) of the epoxy type connected to the polyorganosiloxane backbone B2, of those of following formulae:

As regards the organofunctional groups (Brf) of the alkenyl ether type connected to the polyorganosiloxane backbone B2, mention may be made of those present in the following formulae: O)_(n′)—(CH₂)_(n′)—O—CH═CH₂ —(O)_(n′)—(CH₂)_(n′)—R⁸—O—CH═CH₂ —(O)_(n′)—(CH₂)_(n′)—O—CH═CH—R⁹ in which:

-   -   n′ represents 0 or 1 and n″ an integer between 1 and 5     -   R⁸ represents:         -   a linear, branched or cyclic C₁-C₁₂ alkylene radical which             is optionally substituted,         -   or a C₅-C₁₂ arylene radical, preferably a phenylene radical,             which is optionally substituted, preferably by one to three             C₁-C₆ alkyl groups,     -   R⁹ represents a linear or branched C₁-C₆ alkyl radical.

As regards the organofunctional dioxolane groups (Brf) alkenyl ether connected to the polyorganosiloxane backbone B2, mention may be made of those present in the following formulae:

The polyorganosiloxanes B2 with epoxy, dioxolane or alkenyl ether functional groups (Brf) are generally provided in the form of fluids exhibiting a viscosity at 25° C. of 10 to 10 000 mm²/s and preferably of 20 to 600 mm²/s.

The dynamic viscosity at 25° C. of all the silicones considered in the present description can be measured using a Brookfield viscometer, according to Standard AFNOR NFT 76 102 of February 1972.

The alkenyl ether functional polyorganosiloxanes B2 can be prepared by a hydrosilylation reaction between oils comprising Si—H units and vinyloxy functional compounds, such as allyl vinyl ether or allylvinyloxyethoxybenzene.

The epoxy functional polyorganosiloxanes B2 can be prepared by a hydrosilylation reaction between oils comprising Si—H units and epoxy functional compounds, such as 4-vinylcyclohexene oxide, allyl glycidyl ether, and the like.

The dioxolane functional polyorganosiloxanes B2 can be prepared by hydrosilylation of unsaturated dioxolanes.

The polyorganosiloxanes B2 corresponding best to the subject matter of the invention are described in the formulae hereinbelow and have at least one epoxide, alkenyl ether or oxetane group. X can represent an alkyl, cyclohexyl, trifluoropropyl, perfluoroalkyl, alkoxy or hydroxypropyl group, R can represent a C₁ to C₁₀ alkyl, cyclohexyl, trifluoropropyl or C₁ to C₁₀ perfluoroalkyl radical and (0≦a≦1 000); (1≦b≦1 000).

The initiation of the polymerization and/or crosslinking stage according to the invention is carried out by virtue of the presence of the initiator system C, which is either cationic or cationic and radical.

The cationic initiators can be chosen from onium borates (taken on their own or as a mixture of them), the onium being that of an element from Groups 15 to 17 of the Periodic Table [Chem. & Eng. News, Vol. 63, No. 5, 26, of Feb. 4, 1985], or borates of an organometallic complex of an element from Groups 4 to 10 of the Periodic Table [same reference].

The cationic entity of the cationic initiator is selected from:

-   1) onium salts of formula (VI):     [(R¹⁰)_(n)-A-(R¹¹)_(m)]⁺  (VI)     in which:     -   A represents an element from Groups 15 to 17, such as, for         example: I, S, Se, P or N,     -   R¹⁰ represents a C₆-C₂₀ carbocyclic or heterocyclic aryl         radical, it being possible for said heterocyclic radical to         comprise nitrogen or sulfur as heteroelements,     -   R¹¹ represents R¹⁰ or a linear or branched C₁-C₃₀ alkyl or         alkenyl radical; said R¹⁰ and R¹¹ radicals optionally being         substituted by a C₁-C₂₅ alkoxy, C₁-C₂₅ alkyl, nitro, chloro,         bromo, cyano, carboxyl, ester or mercapto group,     -   n is an integer ranging from 1 to v+1, v being the valency of         the element A,     -   m is an integer ranging from 0 to v−1, with n+m=v+1, -   2) the oxoisothiochromanium salts disclosed in patent application WO     90/11303, in particular the sulfonium salt of     2-ethyl-4-oxoisothiochromanium or of     2-dodecyl-4-oxoisothiochromanium, -   3) sulfonium salts in which the cationic entity comprises:     -   3₁ at least one polysulfonium species of formula VIII.1:     -    in which:         -   the Ar¹ symbols, which are identical or different, each             represent a monovalent aromatic radical (for example: phenyl             or naphthyl) optionally substituted with one or more             radicals chosen from: (i) a linear or branched C₁-C₁₂,             preferably C₁-C₆, alkyl radical, (ii) a linear or branched             C₁-C₁₂ alkoxy radical optionally substituted by an —OH             group, preferably a C₁-C₆ alkoxy radical, (iii) a halogen             atom, (iv) an —OH group, (v) a —COOH group, (vi) a             —COO-alkyl ester group, where the alkyl part is a linear or             branched C₁-C₁₂, preferably C₁-C₆, residue, and (vii) a             group of formula —Y⁴—Ar², where the Y⁴ and Ar² symbols have             the meanings given immediately below,         -   the Ar² symbols, which are identical or different, each             represent a monovalent aromatic radical (for example: phenyl             or naphthyl) optionally substituted with one or more             radicals chosen from: (i) a linear or branched C₁-C₁₂ alkyl             radical optionally substituted by an —OH group, preferably a             C₁-C₆ alkyl radical, (ii) a linear or branched C₁-C₁₂,             preferably C₁-C₆, alkoxy radical, (iii) a halogen atom, (iv)             an —OH group, (v) a —COOH group, (vi) a —COO-alkyl ester             group, where the alkyl part is a linear or branched C₁-C₁₂,             preferably C₁-C₆, residue, the Ar³ symbols, which are             identical or different, each represent a divalent phenylene             or naphthalene radical optionally substituted with one or             more radicals chosen from: (i) a linear or branched C₁-C₁₂,             preferably C₁-C₆, alkyl radical, (ii) a linear or branched             C₁-C₁₂, preferably C₁-C₆, alkoxy radical, (iii) a halogen             atom, (iv) an —OH group, (v) a —COOH group, (vi) a             —COO-alkyl ester group, where the alkyl part is a linear or             branched C₁-C₁₂, preferably C₁-C₆, residue,         -   t is an integer equal to 0 or 1, with the additional             conditions according to which:             -   when t=0, the Y symbol is then a Y¹ monovalent radical                 representing the group of formula:             -    where the Ar¹ and Ar² symbols have the meanings given                 above,             -   when t=1:                 -   on the one hand, the Y symbol is then a divalent                     radical having the following meanings Y² to Y⁴:                 -    Y²: a group of formula:                 -    where the Ar² symbol has the meanings given above,                 -    Y³: a single valency bond,                 -    Y⁴: a divalent residue chosen from:                 -    a linear or branched C₁-C₁₂, preferably C₁-C₆,                     alkylene residue and a residue of formula                     —Si(CH₃)₂O—,                 -   on the other hand, solely in the case where the Y                     symbol represents Y³ or Y⁴, the Ar¹ and Ar²                     (terminal) radicals have, in addition to the                     meanings given above, the possibility of being                     connected to one another via the Y′ residue                     consisting of Y′¹ a single valency bond, or of Y′²,                     a divalent residue chosen from the residues cited                     with respect to the definition of Y⁴, which is                     inserted between the carbon atoms, facing each                     other, situated on each aromatic ring in the ortho                     position with respect to the carbon atom connected                     directly to the S⁺ cation;     -   3₂ at least one monosulfonium species having a single S⁺         cationic center per mole of cation and comprising, in the         majority of cases, species of formulae:         in which formula Ar¹ and Ar² have the meanings given above with         respect to the formula (VIII.1), including the possibility of         directly connecting between them only one of the Ar¹ radicals to         Ar² according to the manner indicated above with respect to the         definition of the additional condition in force when t=1 in the         formula (II) involving the Y′ residue;     -   3₃ and/or at least one monosulfonium species having a single S⁺         cationic center per mole of cation and of formulae:         -   in which R₁₄, R₁₅ and R₁₆, which are identical or different,             represent (i) a hydrogen atom, (ii) a halogen atom (for             example fluorine), (iii) a linear or branched C₁-C₃₀ alkyl             radical which can be substituted by at least one halogen             (for example fluorine), (iv) an —OH radical, (v) an             —O—C(═O)—R radical where R is a linear or branched C₁-C₃₀             alkyl radical which can be substituted by at least one             halogen (for example fluorine), (vi) an OR′ alkoxy radical             where R′ is a linear or branched C₁-C₃₀ alkyl radical which             can be substituted by at least one halogen (for example             fluorine), -   4) the sulfoxonium salts S⁺═O corresponding to the sulfonium     salts 3) described in the preceding paragraph, -   5) organometallic salts of formula (IX):     (L¹L²L³M)^(q+)  (IX)     in which formula:     -   M represents a metal from the Group 4 to 10, in particular iron,         manganese, chromium or cobalt,     -   L¹ represents 1 ligand bonded to the metal M via π electrons,         which ligand is chosen from η³-alkyl, η⁵-cyclopendadienyl and         η⁷-cycloheptratrienyl ligands and η⁶-aromatic compounds chosen         from optionally substituted η⁶-benzene ligands and compounds         having from 2 to 4 condensed rings, each ring being capable of         contributing to the valency layer of the metal M via 3 to 8 π         electrons;     -   L² represents a ligand bonded to the metal M via π electrons,         which ligand is chosen from η⁷-cycloheptatrienyl ligands and         η⁶-aromatic compounds chosen from optionally substituted         η⁶-benzene ligands and compounds having from 2 to 4 condensed         rings, each ring being capable of contributing to the valency         layer of the metal M via 6 or 7 π electrons;     -   L³ represents from 0 to 3 identical or different ligands bonded         to the metal M via σ electrons, which ligand(s) is (are) chosen         from CO and NO₂ ⁺; the total electronic charge q of the complex         to which L¹, L² and L³ and the ionic charge of the metal M         contribute being positive and equal to 1 or 2.

The borate anionic entity of the cationic initiator has the formula (X): [BX″_(a)R¹² _(b)]⁻  (X) in which:

-   -   a and b are integers ranging from 0 to 3 for a and from 1 to 4         for b, with a+b=4,     -   the X″ symbols represent:         -   a halogen atom (chlorine or fluorine) with a=0 to 3,         -   an OH functional group with a=0 to 2,     -   the R¹² symbols, which are identical or different, represent:         -   a phenyl radical substituted by at least one             electron-withdrawing group, such as, for example, OCF₃, CF₃,             NO₂ or CN, and/or by at least 2 halogen atoms (very             particularly fluorine), this being when the cationic entity             is an onium of an element from Groups 15 to 17,         -   a phenyl radical substituted by at least one             electron-withdrawing element or group, in particular a             halogen atom (very particularly fluorine), CF₃, OCF₃, NO₂ or             CN, this being when the cationic entity is an organometallic             complex of an element from Groups 4 to 10,         -   an aryl radical comprising at least two aromatic nuclei,             such as, for example, biphenyl or naphthyl, which is             optionally substituted by at least one electron-withdrawing             element or group, in particular a halogen atom (very             particularly fluorine), OCF₃, CF₃, NO₂ or CN, whatever the             cationic entity.

According to a first preferred form, the cationic initiator is chosen from the onium salts of a cationic entity of formula (VI) and of an anionic entity of formula (X).

According to a second preferred form, the cationic initiator is chosen more specifically from the initiator subclasses described hereinbelow.

Thus, the borate anionic entity is preferably chosen from anions of formula [BF_(a)R¹² _(b)]⁻ in which the R¹² symbols, which are identical or different, represent a phenyl radical substituted by at least one electron-withdrawing group chosen from OCF₃, CF₃, NO₂ and CN and/or by at least two fluorine atoms.

More specifically, the anions which are very particularly suitable are the following:

1′: [B(C₆F₅)₄]⁻ 5′: [B(C₆H₃(CF₃)₂)₄]⁻ 2′: [(C₆F₅)₂BF₂]⁻ 6′: [B(C₆H₃F₂)₄]⁻ 3′: [B(C₆H₄CF₃)₄]⁻ 7′: [C₆F₅BF₃]⁻ 4′: [B(C₆F₄OCF₃)₄]⁻

As regards the cationic entity of the initiator which can in particular be associated with a borate anionic entity and in particular with a borate anionic entity of formula [BF_(a)R¹² _(b)]⁻, five families are distinguished:

1) onium salts of formula (VI), 2) oxoisothiochromanium salts of formula (VII), 3) mono- and/or polysulfonium salts, in particular of formulae (VIII.1) to (VIII.5), 4) sulfoxonium salts, 5) and organometallic salts of formula (IX).

The first family 1) is disclosed in numerous documents, in particular in patents U.S. Pat. Nos. 4,026,705, 4,032,673, 4,069,056, 4,136,102 and 4,173,476. The following cations will very particularly be favored among these:

-   [C₈H₁₇—O-Φ-I-Φ-CH₃]⁺ [(Φ-CH₃)₂I]⁺ -   [C₁₂H₂₅-Φ-I-Φ-C(CH₃)₃]⁺ [(C₈H₁₇—O-Φ)₂I]⁺ -   [(C₈H₁₇—O-Φ-I-Φ)]⁺ [(CH₃Φ)₃S]⁺ -   [(CH₃Φ)₂—S-Φ-O—C₈H₁₇]⁺ [(CH₃-Φ-I-Φ-CH(CH₃)₂]⁺ -   [(CH₃Φ-S-ΦS-(ΦCH₃)₂]⁺ [(C₁₂H₂₅-Φ)₂I]⁺ -   [(CH₃-Φ-I-Φ-OC₂H₅]⁺ [C₁₂H₂₅-Φ-I-Φ-CH₃]⁺ -   and [(CH₃)₃C-Φ-I-Φ-C(CH₃)₃]⁺

As regards the second family 2) of cationic entities of formula (VII) and of oxoisothiochromanium type, it preferably comprises cations corresponding to the structure DI which is defined on page 14 of application WO-A-90/11303 and has the formula (VII):

where the R¹³ radical has the meaning given in this WO application with respect to the R¹ symbol; a cationic entity of this type which is more preferred is that where R¹³ represents a linear or branched C₁-C₂₀ alkyl radical. Mention will particularly be made, as oxoisothiochromanium salts which are particularly well suited, of the sulfonium salt of 2-ethyl-4-oxoisothiochromanium or of 2-dodecyl-4-oxoisothiochromanium.

As regards the cationic sulfonium entities of the family 3), it will be specified that the cationic entity preferably comprises at least one of the following species:

As regards the fifth type of cationic entity (IX), it is found disclosed in patent U.S. Pat. Nos. 4,973,722 and 4,992,572 and European patent applications EP-A-203 829, EP-A-323 584 and EP-A-354 181. The organometallic salts more readily used in practice are in particular:

-   -   (η⁵-cyclopentadienyl) (η⁶-toluene)Fe⁺,     -   (η⁵-cyclopentadienyl) (η⁶-1-methyl-naphthalene)Fe⁺,     -   (η⁵-cyclopentadienyl) (η⁶-cumene)Fe⁺,     -   bis(η⁶-mesitylene)Fe⁺,     -   bis(η⁶-benzene)Cr⁺.

Mention will be made, as examples of preferred initiators of the onium borates type, of the following products:

-   [C₈H₁₇—O-Φ-I-Φ-CH₃]⁺ [B(C₆F₅)₄]⁺ (C₈H₁₇)—O-Φ-I-Φ(C₁₂H₂₅)]⁺     [B(C₆F₅)₄]⁻ -   [C₁₂H₂₅-Φ-I-Φ(CH₃)]⁺ [B(C₆F₅)₄]⁻ [(C₈H₁₇—O-Φ)₂I]⁺ [B(C₆F₅)₄]⁻ -   [(C₈H₁₇)—O-Φ-I-ΦCH(CH₃)₂]⁺ [B(C₆F₅)₄] [(CH₃Φ)₃S]⁺ [B(C₆F₅)₄]⁻ -   [(CH₃Φ)₂S-Φ-O—C₈H₁₇]⁺ [B(C₆H₄CF₃)₄]⁻ [(C₁₂H₂₅-Φ)₂I]⁺ [B(C₆F₅)₄]⁻ -   [(CH₃Φ)₃S]⁺ [B(C₆H₃(m-CF₃)₂)₄]⁻ [(Φ-CH₃)₂I]⁺ [B(C₆F₅)₄]⁻ -   [(CH₃Φ)₃S]⁺ [B(C₆H₃(m-CF₃)₂)₄]⁻ [CH₃-Φ-I-Φ-CH(CH₃)₂]⁺ [B(C₆F₅)₄]⁻ -   [CH₃-Φ-I-Φ-CH(CH₃)₂]⁺ [B(C₆F₅)₄]⁻ -   (η⁵-cyclopentadienyl) (η⁶-toluene)Fe⁺[B (C₆F₅)₄]⁻ -   (η⁵-cyclopentadienyl) (η⁶-1-methylnaphthalene)-Fe⁺[B(C₆F₅)₄]⁻ -   and (η⁵-cyclopentadienyl) (η⁶-cumene)Fe⁺[(B(C₆F₅)₄]⁻.

Mention may be made, as other literature reference in defining the onium borates 1) and the oxoisothiochromanium borates 2) and the borates of organometallic salts 5), which are selected as initiator in the context of the invention, of the entire contents of patent applications EP 562 897 and EP 562 922. These contents are incorporated in full by reference in the present account.

Mention may be made, as other example of an onium salt which can be used within the initiator system C, of those disclosed in U.S. Pat. Nos. 4,138,255 and 4,310,469 (Crivello)

Use may also be made of other cationic initiators; e.g. those sold by Union Carbide (photoinitiator 6990 and 6974 triarylsulfonium hexafluorophosphate and hexafluoroantimonate), iodonium hexafluorophosphate or hexafluoroantimonate salts, or the ferrocenium salts of these various anions.

The radical initiators capable of being used within the initiator systems C are based on benzophenones. Mention may be made, by way of examples, of those sold by Ciba-Geigy: Irgacure 184, Irgacure 500, Darocure 1173, Irgacure 1700, Darocure 4265, Irgacure 907, Irgacure 369, Irgacure 261, Irgacure 784 DO, Irgacure 2959 and Irgacure 651.

The radical initiators can comprise one or more phosphorus atoms, such as those sold by Ciba-Geigy (Irgacure 1700) or BASF (Lucirin TPO).

The initiator system C is advantageously employed in solution in an organic solvent (accelerator), preferably chosen from proton donors and more preferably still from the following groups: isopropyl alcohols, benzyl alcohols, diacetone alcohol, butyl lactate and their mixtures. The photoinitiator C can also be employed directly by dissolving in the matrix A and/or B.

The term “effective amount of initiator system” is understood to mean, within the meaning of the invention, the amount sufficient to initiate the crosslinking. This effective amount advantageously corresponds to 1×10⁻⁶ to 1, preferably from 1×10⁻⁵ to 1×10⁻¹ and more preferably still from 1×10⁻⁴ to 1×10⁻² mol of initiator system per 1 mol of Arf and Brf.

The treatment composition according to the invention can also comprise at least one (photo)-sensitizer D. This is because, to overcome possible disadvantages related to the structure of the plastics, to the treatment composition according to the invention, to the type of activation used and/or to the intrinsic inhibiting properties of certain packagings (thick coating and/or plastic, coating and/or plastic with pigments and the like), the use of a (photo)-sensitizer D proves to be very beneficial.

By way of examples, the photosensitizer D can be selected from (poly)aromatic products, which are optionally metallic, and heterocyclic products and preferably chosen from the list of following products: phenothiazine, tetracene, perylene, anthracene, 9,10-diphenylanthracene, thioxanthone, 2-chlorothioxanthen-9-one, 1-chloro-4-propoxy-9H-thioxanthen-9-one, isopropyl-OH-thioxanten-9-one, mixture of 2- and 4-isomers, 2-isopropyl-9H-thioxanthen-9-one, benzophenone, [4-(4-methylphenylthio)phenyl]phenyl-methanone, 4-benzyl-4′-methyldiphenyl sulfide, acetophenone, xanthone, fluorenone, anthraquinone, 9,10-dimethylanthracene, 2-ethyl-9,10-dimethyloxyanthracene, 2,6-dimethylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, xanthopinacol, 1,2-benzanthracene, 9-nitroanthracene, and their mixtures.

Mention will be made, among the pigments E capable of being present within the treatment composition, of, for example, the following products: titanium dioxide, kaolin, calcium carbonate, black iron oxide, nitrogenous barium salts, aluminum pigments, calcium borosilicate, carbanzole violet, azo pigments, red iron oxide, yellow iron oxide, diazo, naphthol, carbon black, bayrite, dianisidine, monoarylide, pyrazolone, toluidine, calcium red, nitrogenous Ca salts, nitrogenous Ba salts, diarylide, monoarylide, phthalocyanine, benzimidazoline, bronze powder or rhodamine.

Other additives can also be used. Mention may be made, by way of examples, of dyes, fillers (silicone or nonsilicone), surfactants, inorganic reinforcing fillers (siliceous or nonsiliceous), bactericides, corrosion inhibitors, binding bases, organosilicon compounds or epoxide compounds, such as alkoxysilanes, epoxycycloaliphatic compounds or epoxyetheraliphatic compounds.

In addition to the various components cited previously, the compositions of the treatment process according to the invention can comprise a stabilization additive based on a tertiary, secondary or primary aliphatic amine and preferably chosen from the derivatives disclosed in patent application WO98/07798.

EXAMPLES

The examples which follow will make possible a better understanding of the invention and will make it possible to bring out all its advantages and to glimpse some of its alternative embodiments.

Example 1

Formulation

A formulation according to the invention respectively comprises, by mass:

-   -   80 g of silicone oil H1 with a viscosity of 200 mPa.s, with the         following formula where a=10:     -   20 g of oxetane O1 of formula:     -   and 2.5 g of an 18% solution of Rhodorsil® Photoinitiator 2074         in isopropanol.         Tests

The formulation is applied in a proportion of 10 g/m² to transparent polypropylene plaques with a thickness of 500 μm positioned horizontally.

Polymerization is carried out by irradiation using a 180 W/cm Hg/Ga lamp from IST at a rate of 50 m/min.

The adhesion of the coating obtained is evaluated by measuring the attachment of the polymerized formulation according to a standardized “right-angle lattice pattern” test according to Standard EN ISO 2409. A value of 0 corresponds to perfect adhesion and a value of 5 corresponds to zero adhesion.

Results

The attachment of the polymerized formulation is of very good quality (value equal to 0 according to Standard EN ISO 2409).

Example 2

Formulation

A photocrosslinkable formulation for a nonstick coating including a phthalocyanine blue, pigment of Sunfast Blue 15:30 type is prepared according to the procedure below.

A concentrated pigment base CPB is obtained by dispersion of 50 parts of phthalocyanine blue and 100 parts of the silicone oil H1 in a reactor with a capacity of 500 ml equipped with a central three-bladed stirrer.

After mixing for 30 minutes, the concentrated pigment base CPB is milled on a three-roll mill so as to obtain a dispersion with a midnight blue color and with a particle size of less than 10 μm.

Subsequently, the following are added and mixed with 10 g of-concentrated pigment base: 70 g of silicone oil H1, 20 g of oxetane O1, 2 g of a 50% solution of initiator Rhodorsil® Photoinitiator 2074 in oxetane O1, and 0.5 g of isopropylthioxanthone.

Tests and Results

The quality of the nonstick coating is evaluated on a UV device from IST equipped with two 200 W/cm Hg lamps doped with Ga on a polypropylene plaque (thickness of 500 micrometers).

The formulation is polymerized over a thickness of two micrometers at a rate of 50 m/min.

The adhesion of the coating to the polypropylene plaque, evaluated by measuring the attachment to the support, is considered to be excellent.

The coating is water-resistant.

The hardness of the coating is evaluated according to the pencil hardness test and is at least equal to HB immediately after irradiation of the formulation. 

1. A process for the surface treatment of a plastic comprising the following stages: (1) application, to at least one of the surfaces of the plastic, of a composition with polymerizable and/or crosslinkable reactive functional groups comprising: 1 to 99% by weight, of at least one polymerizable and/or at least partially polymerized silicone matrix A comprising (co)monomers, (co)oligomers and/or (co)polymers of at least one polyorganosiloxane species A1), which (co)monomers, (co)oligomers and/or (co)polymers comprise units of formula (II) and are terminated by units of formula (III) or are cyclic and comprise units of formula (II), which formulae are represented below:

 in which: the R⁶ and R⁷ symbols, which are alike or different, represent: a linear or branched alkyl radical comprising 1 to 8 carbon atoms which is optionally substituted by at least one halogen, the alkyl radicals, a cycloalkyl radical comprising between 5 and 8 carbon atoms, which radical is optionally substituted, an aryl radical comprising between 6 and 12 carbon atoms, which radical can be substituted, an aralkyl radical having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part comprising between 6 and 12 carbon atoms, which part is optionally substituted on the aryl part by halogens, alkyls and/or alkoxyls comprising 1 to 3 carbon atoms, the Z symbols, which are alike or different, represent: an R⁶ and/or R⁷ group, a hydrogen radical, and/or a crosslinkable oxetane functional group connected to the silicon of the polyorganosiloxane via a divalent radical which comprises from 2 to 20 carbon atoms and which can comprise at least one heteroatom, it being possible for the latter to be bonded directly to the silicon, forming an ≡Si—OC≡ bond, with at least one of the Z symbols representing a crosslinkable oxetane functional group, 99 to 1% by weight, of at least one polymerizable and/or at least partially polymerized matrix B comprising (co)monomers, (co)oligomers and/or (co)polymers selected from those having epoxy (α₁) and/or acrylate (α₂) and/or alkenyl ether (α₃) and/or hydroxyl (α₄) reactive functional groups (Brf), an effective amount of at least one cationic or cationic and radical initiator system C, optionally at least one sensitizer D, and optionally at least one pigment E; (2) and polymerization and/or crosslinking of the treated surface by its exposure under a source of irradiation and/or under electron beam(s), wherein the matrix B comprises at least one of the following organic species BI: (α₁) epoxides or noncycloaliphatic epoxides, (α₂) acrylates, (α₃) linear or cyclic alkenyl ethers, and (α₄) and polyols, wherein the organic species B1 is selected from the group consisting of: α_(1.1)) cycloaliphatic epoxides comprising: epoxides of the 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate:

or bis(3,4-epoxycyclohexyl) adipate; α_(1.2)) noncycloaliphatic epoxides comprising: epoxides resulting from the condensation of bisphenol A and of epichiorohydrin and: di- and triglycidyl ethers of bisphenol A alkoxylated with 1,6-hexanediol, with glycerol, with neopentyl glycol and with trimethyloipropane, or diglycidyl ethers of bisphenol A, α-olefin epoxides, novolac epoxides, epoxidized soybean oil, epoxidized linseed oil and epoxidized polybutadiene, α₂) acrylates, comprising: epoxidized acrylates, polyester glycerol acrylates, multifunctional acrylates comprising pentaerythritol triacrylate (PETA), trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDODA), trimethylolpropane ethoxylate triacrylate, thiodiethylene glycol diacrylate, tetraethylene glycol diacrylate (TTEGDA), tripropylene glycol diacrylate (TRPGDA), triethylene glycol diacrylate (TREGDA) or trimethylpropane trimethacrylate (TMPTMA), urethane acrylates, polyether acrylates, polyester acrylates, unsaturated polyesters, acrylic acrylates, α₃) linear or cyclic alkenyl ethers comprising: vinyl ethers comprising dodecyl vinyl ether (DDVE), cyclohexyl vinyl ether (CVE), butanediol divinyl ether (BOVE), butanediol monovinyl ether (HBVE), cyclohexanedimethanol d ivinyl ether (CHDVE), cyclohexanedimethanol monovinyl ether (CHMVE), triethylene glycol divinyl ether (DVE-3) or vinyl ethers of formulae:

propenyl ethers, and butenyl ethers; α₄) polyols.
 2. The process as claimed in claim 1, wherein the initiator C is a cationic initiator, the anionic entity of which is a borate of formula (X): [BX″_(a)R² _(b)]⁻  (X) in which: a and b are integers ranging from 0 to 3 for a and from 1 to 4 for b, with a+b=4, the X″ symbols represent: a halogen atom with a=0 to 3, or an OH functional group with a=0 to 2, the R¹² symbols, which are identical or different, represent: a phenyl radical substituted by at least one electron-withdrawing group, and/or by at least 2 halogen atoms, this being when the cationic entity is an onium of an element from Groups 15 to 17 of the Periodic Table, a phenyl radical substituted by at least one electron-withdrawing group, this being when the cationic entity is an organometallic complex of an element from Groups 4 to 10 of the Periodic Table, an aryl radical comprising at least two aromatic nuclei, which is optionally substituted by at least one electron-withdrawing group.
 3. The process as claimed in claim 1, wherein the matrix B comprises at least one monomer(s) and/or oligomer(s) and/or polymer(s) of polyorganosiloxane B2, which monomer(s) and/or oligomer(s) and/or polymer(s) comprise units of formula (IV) and are terminated by units of formula (V) or are cyclic and comprise units of formula (IV), which formulae are represented below:

in which: R⁶ and R⁷ are alike or different, and represent (i) a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, which radical is optionally substituted by at least one halogen; (ii) a cycloalkyl radical comprising between 5 and 8 cyclic carbon atoms, which radical is optionally substituted; (iii) an aryl radical comprising between 6 and 12 carbon atoms, which radical is optionally substituted; (iv) an aralkyl radical having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part comprising between 6 and 12 carbon atoms, which part is optionally substituted on the aryl part by at least one of a halogen, an alkyl, and an alkoxyl comprising 1 to 3 carbon atoms, the Z′ symbols, which are alike or different, represent: an R⁶ and/or R⁷ group, a hydrogen radical, and/or a crosslinkable organofunctional group comprising an epoxy functional, dioxolane functional and/or alkenyl ether functional group, connected at the silicon of the polyorganosiloxane via a divalent radical which comprises from 2 to 20 carbon atoms and which can comprise at least one heteroatom, with at least one of the Z′ symbols representing a crosslinkable organic functional group.
 4. A treated plastic obtained by the process as claimed in claim
 1. 5. The plastic as claimed in claim 4, wherein the surface treatment forms a coating comprising an ink, a nonstick coating, an adhesive coating or a varnish.
 6. A coating obtained by the process as claimed in claim
 1. 7. The coating as claimed in claim 6, wherein the coating is an ink, a nonstick coating, an adhesive coating or a varnish.
 8. A process for the surface treatment of a plastic comprising the following stages: (1) application, to at least one of the surfaces of the plastic, of a composition with polymerizable and/or crosslinkable reactive functional groups comprising: 1 to 99% by weight, of at least one polymerizable and/or at least partially polymerized silicone matrix A comprising (co)monomers, (co)oligomers and/or (co)polymers of at least one polyorganosiloxane species A1), which (co)monomers, (co)oligomers andlor (co)polymers comprise units of formula (II) and are terminated by units of formula (III) or are cyclic and comprise units of formula (II), which formulae are represented below:

 in which: the R⁶ and R⁷ symbols, which are alike or different, represent: a linear or branched alkyl radical comprising 1 to 8 carbon atoms which is optionally substituted by at least one halogen, the alkyl radicals, a cycloalkyl radical comprising between 5 and 8 carbon atoms, which radical is optionally substituted, an aryl radical comprising between 6 and 12 carbon atoms, which radical can be substituted, an aralkyl radical having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part comprising between 6 and 12 carbon atoms, which part is optionally substituted on the aryl part by halogens, alkyls and/or alkoxyls comprising 1 to 3 carbon atoms, the Z symbols, which are alike or different, represent: an R⁶ and/or R⁷ group, a hydrogen radical, and/or a crosslinkable oxetane functional group connected to the silicon of the polyorganosiloxane via a divalent radical which comprises from 2 to 20 carbon atoms and which can comprise at least one heteroatom, it being possible for the latter to be bonded directly to the silicon, forming an ≡Si—OC≡ bond, with at least one of the Z symbols representing a crosslinkable oxetane functional group, 99 to 1% by weight, of at least one polymerizable and/or at least partially polymerized matrix B comprising (co)monomers, (co)oligomers and/or (co)polymers selected from those having epoxy (α₁) and/or acrylate (α₂) and/or alkenyl ether (α₃) and/or hydroxyl (α₄) reactive functional groups (Brf), an effective amount of at least one cationic or cationic and radical initiator system C, optionally at least one sensitizer D, and optionally at least one pigment E; (2) and polymerization and/or crosslinking of the treated surface by its exposure under a source of irradiation and/or under electron beam(s), wherein the silicone matrix A additionally comprises at least one of the following (co)monomers and/or (co)oligomers and/or (co)polymers comprising at least one of the following organic species: A2) monomers with oxetane and alkoxy functional groups oxetane and hydroxyl functional groups, or oxetane and alkoxysilyl functional groups of formula:

in which: R₁ is (i) a hydrogen atom; (ii) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms; (iii) an aryl radical comprising from 6 to 30 carbon atoms, which radical is optionally substituted by at least one fluorine atom, one carboxyl radical, one hydroxyl radical, one ester radical or one radical with a ketone functional group; (iv) a cycloalkyl radical comprising from 5 to 6 carbon atoms, which radical is optionally substituted by at least one fluorine atom, one hydroxyl radical, one carboxyl radical, one ester radical or one radical with a ketone functional group; (v) an OR′ radical where R′ is a linear or branched alkyl radical comprising from 1 to 30 carbon atoms; or (vi) an alkenyl radical comprising from 2 to 12 carbon atoms, R₂ is (i) a hydrogen atom: (ii) an alkenyl radical comprising from 2 to 12 carbon atoms; (iii) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, which radical is optionally substituted; (iv) an aryl radical comprising from 6 to 30 carbon atoms, which radical is optionally substituted with at least one alkyl radical comprising from 1 to 30 carbon atoms, one benzyl radical, one CF₃ radical, one halogen atom, one hydroxyl radical, one carboxyl radical or one alkoxy radical; (v) a linear or branched alkylated and silylated or silylated group —(C_(n)H_(2n))—SiR₃R₄R₅, where n is between 0 and 12 and R₃, R₄ and R₅, which are identical or different, represent a hydrogen atom, a hydroxyl radical or an alkoxy radical OR′ where R′ is a linear or branched alkyl radical comprising from 1 to 30 carbon atoms; (vi) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms; (vii) an aryl radical comprising from 6 to 30 carbon atoms, which radical is optionally substituted; (viii) an alkenyl radical comprising from 2 to 12 carbon atoms; (ix) an acrylate radical; (x) a methacrylate radical; or (xi) a urethane radical —CO—NH—R₁ in which R₁ has the same definition as that given above; A3) monomers comprising carboxyl and oxetane functional groups or comprising oxetane and alkoxysilyl functional groups of formula:

in which: R₁ has a definition identical to that given in A2), R₂ has a definition identical to that given in A2); A4) difunctional oxetane monomers of formula:

 in which: m, which is identical or different, is equal to 0 or 1, R₁ has a definition identical to that given in A2), R₆, a divalent radical, is (i) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms; (ii) an aryl radical comprising from 6 to 30 carbon atoms, which radical is optionally substituted (by at least one alkyl radical comprising from 1 to 30 carbon atoms; (iii) an aryl radical comprising from 6 to 30 carbon atoms; (iv) a cycloalkyl radical comprising from 5 to 30 carbon atoms; (v) a —CH₂—C₆H₁₀—CH₂— radical; (vi) a —CH₂—C₆H₄—CH₂— radical; (vii) a silyl group ═SiR₃R₄ and R₃ and R₄, which are identical or different, represent a hydrogen atom, a hydroxyl radical, an alkoxy radical OR′ where R′ has a definition identical to that given in A2), a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, an aryl radical comprising from 6 to 30 carbon atoms which is optionally substituted, an alkenyl radical comprising from 2 to 12 carbon atoms.
 9. The process as claimed in claim 8, wherein the initiator C is a cationic initiator, the anionic entity of which is a borate of formula (X): [BX″_(a)R¹² _(b)]⁻  (X) in which: a and b are integers ranging from 0 to 3 for a and from 1 to 4 for b, with a+b=4, the X″ symbols represent: a halogen atom with a=0 to 3, or an OH functional group with a=0 to 2, the R¹² symbols, which are identical or different, represent: a phenyl radical substituted by at least one electron-withdrawing group, and/or by at least 2 halogen atoms, this being when the cationic entity is an onium of an element from Groups 15 to 17 of the Periodic Table, a phenyl radical substituted by at least one electron-withdrawing group, this being when the cationic entity is an organometallic complex of an element from Groups 4 to 10 of the Periodic Table, an aryl radical comprising at least two aromatic nuclei, which is optionally substituted by at least one electron-withdrawing group.
 10. The process as claimed in claim 8, wherein the matrix B comprises at least one monomer(s) and/or oligomer(s) and/or polymer(s) of polyorganosiloxane B2, which monomer(s) and/or oligomer(s) and/or polymer(s) comprise units of formula (IV) and are terminated by units of formula (V) or are cyclic and comprise units of formula (IV), which formulae are represented below:

in which: R⁶ and R⁷ are alike or different, and represent (i) a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, which radical is optionally substituted by at least one halogen; (ii) a cycloalkyl radical comprising between 5 and 8 cyclic carbon atoms, which radical is optionally substituted; (iii) an aryl radical comnrising between 6 and 12 carbon atoms, which radical is optionally substituted; (iv) an aralkyl radical having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part comprising between 6 and 12 carbon atoms, which part is optionally substituted on the aryl part by at lest one of a halogen, an alkyl, and an alkoxy comprising 1 to 3 carbon atoms, the Z′ symbols, which are alike or different, represent: an R⁶ and/or R⁷ group, a hydrogen radical, and/or a crosslinkable organofunctional group comprising an epoxy functional, dioxolane functional and/or alkenyl ether functional group, connected at the silicon of the polyorganosiloxane via a divalent radical which comprises from 2 to 20 carbon atoms and which can comprise at least one heteroatom, with at least one of the Z′ symbols representing a crosslinkable organic functional group.
 11. A treated plastic obtained by the process as claimed in claim
 8. 12. The plastic as claimed in claim 11, wherein the surface treatment forms a coating comprising an ink, a nonstick coating, an adhesive coating or a varnish.
 13. A coating obtained by the process as claimed in claim
 8. 14. The coating as claimed in claim 13, wherein the coating is an ink, a nonstick coating, an adhesive coating or a varnish.
 15. A process for the surface treatment of a plastic comprising the following stages: (1) application, to at least one of the surfaces of the plastic, of a composition with polymerizable andlor crosslinkable reactive functional groups comprising: 1 to 99% by weight, of at least one polymerizable and/or at least partially polymerized silicone matrix A comprising (co)monomers, (co)oligomers and/or (co)polymers of at least one polyorganosiloxane species A1), which (co)monomers, (co)oligomers and/or (co)polymers comprise units of formula (II) and are terminated by units of formula (III) or are cyclic and comprise units of formula (II), which formulae are represented below:

 in which: the R⁶ and R⁷ symbols, which are alike or different, represent: a linear or branched alkyl radical comprising 1 to 8 carbon atoms which is optionally substituted by at least one halogen, the alkyl radicals, a cycloalkyl radical comprising between 5 and 8 carbon atoms, which radical is optionally substituted, an aryl radical comprising between 6 and 12 carbon atoms, which radical can be substituted, an aralkyl radical having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part comprising between 6 and 12 carbon atoms, which part is optionally substituted on the aryl part by halogens, alkyls and/or alkoxyls comprising 1 to 3 carbon atoms, the Z symbols, which are alike or different, represent an R⁶ and/or R⁷ group, a hydrogen radical, and/or a crosslinkable oxetane functional group connected to the silicon of the polyorganosiloxane via a divalent radical which comprises from 2 to 20 carbon atoms and which can comprise at least one heteroatom, it being possible for the latter to be bonded directly to the silicon, forming an ≡Si—OC≡ bond, with at least one of the Z symbols representing a crosslinkable oxetane functional group, 99 to 1% by weight, of at least one polymerizable and/or at least partially polymerized matrix B comprising (co)monomers, (co)oligomers and/or (co)polymers selected from those having epoxy (α₁) and/or acrylate (α₂) and/or alkenyl ether (α₃) and/or hydroxyl (α₄) reactive functional groups (Brf), an effective amount of at least one cationic or cationic and radical initiator system C, optionally at least one sensitizer D, and optionally at least one pigment E; (2) and polymerization and/or crosslinking of the treated surface by its exposure under a source of irradiation and/or under electron beam(s), wherein the matrix B comprises at least one monomer(s) and/or oligomer(s) and/or polymer(s) of polyorganosiloxane B2, which monomer(s) and/or oligomer(s) and/or polymer(s) comprise units of formula (IV) and are terminated by units of formula (V) or are cyclic and comprise units of formula (IV), which formulae are represented below:

 in which: R⁶ and R⁷ are alike or different, and represent (i) a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, which radical is optionally substituted by at least one halogen; (ii) a cycloalkyl radical comprising between 5 and 8 cyclic carbon atoms, which radical is optionally substituted; (iii) an aryl radical comprising between 6 and 12 carbon atoms, which radical is optionally substituted; (iv) an aralkyl radical having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part comprising between 6 and 12 carbon atoms, which part is optionally substituted on the aryl part by at least one of a hydrogen, an alkyl, and an alkoxyl comprising 1 to 3 carbon atoms, the Z′ symbols, which are alike or different, represent: an R⁶ and/or R⁷ group, a hydrogen radical, and/or a crosslinkable organofunctional group comprising an epoxy functional, dioxolane functional and/or alkenyl ether functional group, connected at the silicon of the polyorganosiloxane via a divalent radical which comprises from 2 to 20 carbon atoms and which can comprise at least one heteroatom, with at least one of the Z′ symbols representing a crosslinkable organic functional group, wherein (Brf)s of polyorganosiloxane B2 are selected from the group consisting of the radicals:

—(O)_(n′)—(CH₂)_(n″)—O—CH═CH₂, —(O)_(n′)—(CH₂)_(n″)—R⁸—O—CH═CH₂ and —(O)_(n′),—(CH₂)_(n″),—O—CH═CH—R⁹ in which: n′ represents 0 or 1 and n″ an integer between 1 and 5 R⁸ represents: a linear, branched or cyclic C₁-C₁₂ alkylene radical which is optionally substituted, or a C₅-C₁₂ arylene radical which is optionally substituted and R⁹ represents a linear or branched C₁-C₆ alkyl radical.
 16. The process as claimed in claim 15, wherein the initiator C is a cationic initiator, the anionic entity of which is a borate of formula (X): [BX″_(a)R¹² _(b)]⁻  (X) in which: a and b are integers ranging from 0 to 3 for a and from 1 to 4 for b, with a+b=4, the X″ symbols represent: a halogen atom with a=0 to 3, or an OH functional group with a=0 to 2, the R¹² symbols, which are identical or different, represent: a phenyl radical substituted by at least one electron-withdrawing group, and/or by at least 2 halogen atoms, this being when the cationic entity is an onium of an element from Groups 15 to 17 of the Periodic Table, a phenyl radical substituted by at least one electron-withdrawing group, this being when the cationic entity is an organometallic complex of an element from Groups 4 to 10 of the Periodic Table, an aryl radical comprising at least two aromatic nuclei, which is optionally substituted by at least one electron-withdrawing group.
 17. A treated plastic obtained by the process as claimed in claim
 15. 18. The plastic as claimed in claim 17, wherein the surface treatment forms a coating comprising an ink, a nonstick coating, an adhesive coating or a varnish.
 19. A coating obtained by the process as claimed in claim
 15. 20. The coating as claimed in claim 19, wherein the coating is an ink, a nonstick coating, an adhesive coating or a varnish.
 21. A process for the surface treatment of a plastic comprising the following stages: (1) application, to at least one of the surfaces of the plastic, of a composition with polymerizable and/or crosslinkable reactive functional groups comprising: 1 to 99% by weight, of at least one polymerizable and/or at least partially polymerized silicone matrix A comprising (co)monomers, (co)oligomers and/or (co)polymers of at least one polyorganosiloxane species A1), which (co)monomers, (co)oligomers and/or (co)polymers comprise units of formula (II) and are terminated by units of formula (III) or are cyclic and comprise units of formula (II), which formulae are represented below:

 in which: the R⁶ and R⁷ symbols, which are alike or different, represent: a linear or branched alkyl radical comprising 1 to 8 carbon atoms which is optionally substituted by at least one halogen, the alkyl radicals, a cycloalkyl radical comprising between 5 and 8 carbon atoms, which radical is optionally substituted, an aryl radical comprising between 6 and 12 carbon atoms, which radical can be substituted, an aralkyl radical having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part comprising between 6 and 12 carbon atoms, which part is optionally substituted on the aryl part by halogens, alkyls and/or alkoxyls comprising 1 to 3 carbon atoms, the Z symbols, which are alike or different, represent: an R⁶ and/or R⁷ group, a hydrogen radical, and/or a crosslinkable oxetane functional group connected to the silicon of the polyorganosiloxane via a divalent radical which comprises from 2 to 20 carbon atoms and which can comprise at least one heteroatom, it being possible for the latter to be bonded directly to the silicon, forming an ≡Si—OC≡ bond, with at least one of the Z symbols representing a crosslinkable oxetane functional group, 99 to 1% by weight, of at least one polymerizable and/or at least partially polymerized matrix B comprising (co)monomers, (co)oligomers and/or (co)polymers selected from those having epoxy (α₁) and/or acrylate (α₂) and/or alkenyl ether (α₃) and/or hydroxyl (α₄) reactive functional groups (Brf), an effective amount of at least one cationic or cationic and radical initiator system C, optionally at least one sensitizer D, and optionally at least one pigment E; (2) and polymerization and/or crosslinking of the treated surface by its exposure under a source of irradiation and/or under electron beam(s), wherein the matrix B comprises at least one monomer(s) and/or oligomer(s) and/or polymer(s) of polyorganosiloxane B2, which monomer(s) and/or oligomer(s) and/or polymer(s) comprise units of formula (IV) and are terminated by units of formula (V) or are cyclic and comprise units of formula (IV), which formulae are represented below:

in which: R⁶ and R⁷ are alike or different, and represent (i) a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, which radical is optionally substituted by at least one halogen; (ii) a cycloalkyl radical comprising between 5 and 8 cyclic carbon atoms, which radical is optionally substituted; (iii) an aryl radical comprising between 6 and 12 carbon atoms, which radical is optionally substituted; (iv) an aralkyl radical having an alkyl part comprising between 5 and 14 carbon atoms and an aryl part comprising between 6 and 12 carbon atoms, which part is optionally substituted on the aryl part by at least one of a hydrogen, an alkyl, and an alkoxyl comprising 1 to 3 carbon atoms, the Z′ symbols, which are alike or different, represent: an R⁶ and/or R⁷ group, a hydrogen radical, and/or a crosslinkable organofunctional group comprising an epoxy functional, dioxolane functional and/or alkenyl ether functional group, connected at the silicon of the polyorganosiloxane via a divalent radical which comprises from 2 to 20 carbon atoms and which can comprise at least one heteroatom, with at least one of the Z′ symbols representing a crosslinkable organic functional group. 